CN107641185A - A kind of porphyrin conjugation organic framework material and preparation method thereof - Google Patents
A kind of porphyrin conjugation organic framework material and preparation method thereof Download PDFInfo
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- C08G12/00—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
- C08G12/02—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes
- C08G12/26—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with heterocyclic compounds
Abstract
A kind of porphyrin conjugation organic framework material and preparation method thereof, belongs to new material and its preparing technical field.The material is the two-dimensional slice structural material being formed by connecting by construction unit, and construction unit is porphyrin and derivatives of porphyrin, and all by covalent key connection between construction unit, interlayer is intermolecular force.Preparation method in the present invention is using a certain proportion of five-ring heterocycles and more aldehyde as reactant, and polymerisation occurs in the presence of acid with oxidant, and directly obtaining described porphyrin by one kettle way is conjugated organic framework material.The present invention devise it is a kind of can on molecular scale Effective Regulation material structure and the framework material of property, realize porphyrin conjugation organic framework material one-step synthesis.This method is easy to operate, and cost is cheap, easily amplification, the effective basic research and preparation for promoting organic framework material, new possibility is provided for the practical application of organic framework material.
Description
Technical field
The invention belongs to new material design and preparing technical field, and in particular to a kind of porphyrin conjugation organic framework material
Preparation method.
Background technology
The development of material and the mark that application level is civilization of human society degree, and the discovery of new material is people with application
Class society issues licence one of the important impetus of change.The development of metal material greatly improves social productive forces level and promoted
The industrial revolution of 19th century.The popularization of rubber, plastics, fiber Polymer material largely improves our life water
It is flat.With Iijima first observeds in 1991 to clearly carbon nano tube structure (Iijima S.Nature, 1991,354
(6348):56-58), Geim in 2004 peel off to obtain single-layer graphene (Novoselov K S et al., Science, 2004,
306(5696):666-669), the concept such as nano material and low-dimensional materials causes our noegenesis to material substantially
Change.Contemporary society's rapid economic development, urgently need emerging in large numbers for new material.
The structure and properties of material are regulated and controled in molecular atoms aspect, are design of material and the key of synthesis
Problem.Traditional material is limited to its own property and synthetic method, it is difficult to the accuracy controlling of material structure is realized, especially in material
Nanosizing and low-dimensionalization in terms of it is very difficult.Therefore, small-molecule chemical assembling from bottom to top, it is considered to be realize that material can
Control the effective means of synthesis.2005, Omar M.Yaghi et al. reported a kind of borate ester two dimension and are conjugated organic bone first
Frame material, indicate on molecular level to the careful design and arrival (the Adrien P.Cote et in the epoch of synthesis of material
al.,Science,2005,310,1166-1170).The synthesis strategy of organic framework material is based on methodology of organic synthesis, organic
By covalent key connection between small molecule, infinitely extend to obtain regularly arranged framework material in three dimensions.By designing bottom
Thing structure and synthetic method, organic framework material can easily realize the modulation of its chemical constitution, obtain with regular pore structure,
Superhigh specific surface area, the abundant material system for coordinating site.
The structure design of organic framework material has been now subjected to extensive concern with Study of synthesis method.Kuhn et al. is reported
The synthesis of triazine organic framework material and property (Pieree Kuhn et al., J.Am.Chem.Soc.2008,130,
13333-13337)；(Zhu Junjiang etc., the patent publication No. such as Zhu Junjiang：CN103224264A) by this triazine organic framework material
Removal for organic dyestuff in aqueous phase；Yaghi et al. reported the synthesis of three-dimensional covalent organic framework material in 2009
(Fernando J.Uribe-Romo et al.,J.Am.Chem.Soc.2009,131,4570-4571).However, conjugation is organic
The structure design of framework material is not developed sufficiently also, and it is synthesized and separation method is complicated, is related to multistep organic reaction,
The preparation of extensive high quality high yield is difficult to, therefore significantly limit organic framework material answering in practical systems
With.
The content of the invention
It is an object of the invention to overcome general material to be difficult to the problem of accuracy controlling, design one kind is based on covalent key connection
Porphyrin conjugation organic framework material, realize that framework material prepares to regulate and control with chemical constitution in the other controllable precise of molecular level；Together
When overcome current organic framework material synthetic method complicated, it is difficult to realize the bottleneck of extensive preparation and application, propose a kind of porphin
One step of moiety conjugate organic framework material directly synthesizes, and is organic so as to effectively facilitate the production in enormous quantities of organic framework material
The practical application of framework material provides may.
Technical scheme is as follows：
A kind of porphyrin is conjugated organic framework material, it is characterised in that described porphyrin conjugation organic framework material is by tying
The two-dimensional slice structural material that structure unit is formed by connecting, the construction unit are porphyrin and derivatives of porphyrin, between construction unit
All by covalent key connection.
Further, the interior ring hetero atom of the porphyrin and derivatives of porphyrin is the one or more in N, O and S.
Further, the two-dimensional slice structure that the construction unit connects into, the active force between its lamella are intermolecular
Active force.
The preparation method of porphyrin conjugation organic framework material of the present invention, it comprises the following steps：
1) using five-ring heterocycles and more aldehyde as substrate, it is substantially dissolved in organic solvent, adds acid and oxidant is uniform
Mixing；
Wherein the ratio of the amount of the material of five-ring heterocycles and more aldehyde is 1:0.1-1:10；
2) said mixture is reacted under the conditions of temperature is 40-220 DEG C, the reaction time is 30 minutes to 72 hours.
Further, five-ring heterocycles are the one or more in pyrroles, furans and thiophene；More aldehyde are 3 carbon
And more than 3 carbon, there are two or more aldehyde functions.
Further, the acid is formic acid, acetic acid, propionic acid, butyric acid, hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid, trifluoro formic acid
With the one or more in trifluoroacetic acid；The oxidant be air, oxygen, nitrobenzene, dinitro benzene, trinitrobenzen,
One or more in potassium nitrate, sodium nitrate and ammonium nitrate；The organic solvent be methanol, ethanol, propyl alcohol, isopropanol,
Ethylene glycol, propane diols, glycerine, toluene, ethylbenzene, dimethylbenzene, trimethylbenzene, dichloromethane, chloroform, tetrachloromethane, dioxy
One kind or one kind in six rings, tetrahydrofuran, 1-METHYLPYRROLIDONE, N,N-dimethylformamide and DMAC N,N' dimethyl acetamide
More than.
Porphyrin of the present invention conjugation organic framework material realize framework material in the other careful design of molecular level and
Regulation and control, there is the diversity and stability of chemical constitution；Its simple synthetic method is efficient, preparation condition is gentle.The preparation method
Synthetic route is enormously simplify, can effectively realize being prepared on a large scale for porphyrin conjugation organic framework material, obtains high quality
Porphyrin conjugation organic framework material, technique is simple, cost is cheap, is adapted to engineering amplification to be prepared with batch, helps to promote public
Application of family's organic framework material in practical systems, new possibility is provided for the update of material system.
Brief description of the drawings
Fig. 1 is the ESEM photograph that the porphyrin synthesized using pyrroles and terephthalaldehyde as substrate is conjugated organic framework material
Piece.
Fig. 2 is the transmission electron microscope photograph that the porphyrin synthesized using pyrroles and terephthalaldehyde as substrate is conjugated organic framework material
Piece.
Fig. 3 is the high-resolution transmission electricity that the porphyrin synthesized using pyrroles and terephthalaldehyde as substrate is conjugated organic framework material
Mirror photo.
Fig. 4 is the AFM that the porphyrin synthesized using pyrroles and terephthalaldehyde as substrate is conjugated organic framework material
Photo.
Fig. 5 is the infrared spectrum that the porphyrin synthesized using pyrroles and terephthalaldehyde as substrate is conjugated organic framework material.
Fig. 6 is the X-ray diffraction spectrum that the porphyrin synthesized using pyrroles and terephthalaldehyde as substrate is conjugated organic framework material.
Embodiment
Below by several specific embodiments, the present invention is further illustrated.
A kind of porphyrin conjugation organic framework material proposed by the present invention is the two-dimensional slice knot being formed by connecting by construction unit
Structure material, the construction unit are porphyrin and derivatives of porphyrin, all by covalent key connection between construction unit.The porphyrin and
The interior ring hetero atom of derivatives of porphyrin is the one or more in N, O and S.The two-dimensional slice that the construction unit connects into
Structure, the active force between its lamella is intermolecular force.
The preparation method of porphyrin conjugation organic framework material provided by the invention, it comprises the following steps：
1) using five-ring heterocycles and more aldehyde as substrate, it is substantially dissolved in organic solvent, adds acid and oxidant is uniform
Mixing；Wherein the ratio of the amount of the material of five-ring heterocycles and more aldehyde is 1:0.1-1:10；Five-ring heterocycles are generally pyrroles, furans and thiophene
One or more in fen；More aldehyde are more than 3 carbon and 3 carbon, have two or more aldehyde functions；The acid
Using one kind or one in formic acid, acetic acid, propionic acid, butyric acid, hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid, trifluoro formic acid and trifluoroacetic acid
More than kind；The oxidant is in air, oxygen, nitrobenzene, dinitro benzene, trinitrobenzen, potassium nitrate, sodium nitrate and ammonium nitrate
One or more；The organic solvent is methanol, ethanol, propyl alcohol, isopropanol, ethylene glycol, propane diols, glycerine, first
Benzene, ethylbenzene, dimethylbenzene, trimethylbenzene, dichloromethane, chloroform, tetrachloromethane, dioxane, tetrahydrofuran, N- methylpyrroles
One or more in alkanone, N,N-dimethylformamide and DMAC N,N' dimethyl acetamide.
2) said mixture is reacted under the conditions of temperature is 40-220 DEG C, the reaction time is 30 minutes to 72 hours.
Embodiment 1：Nitrogen porphyrin is obtained by one kettle way as substrate using pyrroles and terephthalaldehyde and is conjugated organic framework material.
Weigh and stirred in 13.4g terephthalaldehydes addition 200mL ethanol, is fully transferred to after dissolving in 500mL flasks.To burning
6.9mL pyrroles is added in bottle, 10mL concentrated hydrochloric acids, 5mL nitrobenzene, is stirred lower well mixed.Flask is placed in oil bath pan, kept
Stir, react 12h at 60 DEG C.Products therefrom is washed by filtering, ethanol, dried, and obtains nitrogen porphyrin conjugation organic framework material.
Reaction yield is 98%.
Embodiment 2：The nitrogen porphyrin for obtaining cobalt coordination by one kettle way using pyrroles and MDA as substrate is conjugated organic backbone
Material.
Weigh and stirred in 14.4g MDAs addition 250mL tetrachloromethanes, is fully transferred to after dissolving in 500mL flasks.To burning
13.8mL pyrroles is added in bottle, 5mL trifluoroacetic acids, 2g potassium nitrate, 6g cobalt nitrates, stirs lower fully dissolving.Flask is placed in oil
In bath, it is kept stirring for, reacts 1h at 140 DEG C.Products therefrom is washed by filtering, ethanol, dried, and obtains the nitrogen porphin of cobalt coordination
Moiety conjugate organic framework material.Reaction yield is 94%.
Embodiment 3：Sulphur porphyrin is obtained by one kettle way as substrate using pyrroles, thiophene and terephthalaldehyde and is conjugated organic backbone
Material.
Weigh and stirred in 13.4g terephthalaldehydes, 3.5mL pyrroles, 15mL thiophene addition 150mL isopropanols, fully dissolving
After be transferred in 500mL flasks.150mL acetic acid is added into flask, 3g trinitrobenzens, stirs lower fully dissolving.Flask is placed in
In oil bath pan, it is kept stirring for, reacts 72h at 120 DEG C.Products therefrom is washed by filtering, ethanol, dried, and is obtained sulphur porphyrin and is total to
Yoke organic framework material.Reaction yield is 92%.
Embodiment 4：Oxygen porphyrin is obtained by one kettle way as substrate using pyrroles, furans and terephthalaldehyde and is conjugated organic backbone
Material.
Weigh and stirred in 13.4g terephthalaldehydes, 3.5mL pyrroles, 13mL furans addition 200mL chloroforms, it is fully molten
It is transferred to after solution in 500mL flasks.10mL concentrated hydrochloric acids are added into flask, 150mL acetic acid, 1.6g sodium nitrate, are stirred lower fully molten
Solution.Flask is placed in oil bath pan, is kept stirring for, reacts 36h at 200 DEG C.Products therefrom is washed by filtering, ethanol, dried,
Obtain oxygen porphyrin conjugation organic framework material.Reaction yield is 97%.
Embodiment 5：The nitrogen porphyrin for obtaining iron cooperation by one kettle way using pyrroles and hexandial as substrate is conjugated organic backbone
Material.
Weigh and stirred in 15.0g hexandials addition 200mL toluene, is fully transferred to after dissolving in 500mL flasks.Into flask
7.4mL pyrroles is added, 15mL trifluoro formic acid, 2.5mL trinitrobenzens, 7.6g ferric trichlorides, is stirred lower well mixed.Flask is put
In oil bath pan, it is kept stirring for, reacts 48h at 95 DEG C.Products therefrom is washed by filtering, ethanol, dried, and obtains iron cooperation
Nitrogen porphyrin is conjugated organic framework material.Reaction yield is 95%.
Embodiment 6：Oxygen porphyrin is obtained by one kettle way as substrate using pyrroles, furans and butanedial and is conjugated organic backbone material
Material.
Weigh and stirred in 17.2g butanedial, 6.9mL pyrroles, 23mL furans addition 100mL trimethylbenzenes and 150mL dioxane
Mix, be fully transferred to after dissolving in 500mL flasks.15mL p-methyl benzenesulfonic acids are added into flask, 3.0g potassium nitrate, are filled under stirring
Divide dissolving.Flask is placed in oil bath pan, is kept stirring for, reacts 18h at 150 DEG C.Products therefrom is by filtering, ethanol washs,
Dry, obtain oxygen porphyrin conjugation organic framework material.Reaction yield is 93%.
Embodiment 7：Nitrogen porphyrin is obtained by one kettle way as substrate using pyrroles and diphenyl-dimethanal and is conjugated organic framework material.
Weigh 21.0g diphenyl-dimethanals, 6.9mL pyrroles adds in 180mL 1-METHYLPYRROLIDONEs and stirred, fully dissolving
After be transferred in 500mL flasks.2mL sulfuric acid is added into flask, 5.8g nickel acetates, is sufficiently stirred.Flask is placed in oil bath pan,
It is kept stirring for, is passed through oxygen, reacts 12h at 40 DEG C.Products therefrom is washed by filtering, ethanol, dried, and obtains the nitrogen of nickel cooperation
Porphyrin is conjugated organic framework material.Reaction yield is 98%.
Embodiment 8：Sulphur porphyrin is obtained by one kettle way as substrate using pyrroles, thiophene and glutaraldehyde and is conjugated organic backbone material
Material.
Weigh 18.5g glutaraldehydes, 7.4mL pyrroles, 17.4mL thiophene add 200mLN, in N- dimethyl acetamides, fully
It is transferred to after dissolving in 500mL flasks.15mL concentrated hydrochloric acids are added into flask, 5.0g ammonium nitrate, stir lower fully dissolving.By flask
It is placed in oil bath pan, is kept stirring for, reacts 48h at 70 DEG C.Products therefrom is washed by filtering, ethanol, dried, and obtains sulphur porphyrin
It is conjugated organic framework material.Reaction yield is 93%.
Embodiment 9：Obtaining nitrogen porphyrin conjugation by one kettle way as substrate using pyrroles and 2,4- dimethyl terephthalaldehyde has
Machine framework material.
24.8g2 is weighed, 4- dimethyl terephthalaldehyde, 8.9mL pyrroles add in 200mL glycerine and stirred, fully dissolving
After be transferred in 500mL flasks.5mL trifluoroacetic acid 50mL acetic acid is added into flask, 5mL nitrobenzene, stirs lower fully dissolving.Will
Flask is placed in oil bath pan, is kept stirring for, and reacts 20h at 200 DEG C.Products therefrom is washed by filtering, ethanol, dried, and is obtained
Nitrogen porphyrin is conjugated organic framework material.Reaction yield is 95%.
Claims (8)
1. a kind of porphyrin is conjugated organic framework material, it is characterised in that described porphyrin conjugation organic framework material is by structure
The two-dimensional slice structural material that unit is formed by connecting, the construction unit are porphyrin and derivatives of porphyrin, complete between construction unit
Portion is by covalent key connection.
2. a kind of porphyrin conjugation organic framework material as claimed in claim 1, it is characterised in that the porphyrin and porphyrin derive
The interior ring hetero atom of thing is the one or more in N, O and S.
A kind of 3. porphyrin conjugation organic framework material as claimed in claim 1 or 2, it is characterised in that described two-dimensional slice
Active force between structure is intermolecular force.
4. the preparation method of the porphyrin conjugation organic framework material described in a kind of claim 1, it is characterised in that this method includes
Following steps：
1) using five-ring heterocycles and more aldehyde as substrate, it is substantially dissolved in organic solvent, adds acid and oxidant uniformly mixes；
Wherein the ratio of the amount of the material of five-ring heterocycles and more aldehyde is 1:0.1-1:10；
2) said mixture is reacted under the conditions of temperature is 40-220 DEG C, the reaction time is 30 minutes to 72 hours.
5. the preparation method of a kind of porphyrin conjugation organic framework material as claimed in claim 4, it is characterised in that described five yuan
Heterocycle is the one or more in pyrroles, furans and thiophene；More aldehyde be more than 3 carbon or 3 carbon have two with
Upper aldehyde functions.
6. the preparation method of a kind of porphyrin conjugation organic framework material as claimed in claim 4, it is characterised in that the acid is
Formic acid, acetic acid, propionic acid, butyric acid, hydrochloric acid, sulfuric acid, p-methyl benzenesulfonic acid, trifluoro formic acid and one kind in trifluoroacetic acid or it is a kind of with
On.
A kind of 7. preparation method of porphyrin conjugation organic framework material as claimed in claim 4, it is characterised in that the oxidation
Agent be one kind in air, oxygen, nitrobenzene, dinitro benzene, trinitrobenzen, potassium nitrate, sodium nitrate and ammonium nitrate or it is a kind of with
On.
8. the preparation method of a kind of porphyrin conjugation organic framework material as claimed in claim 4, it is characterised in that described organic
Solvent is methanol, ethanol, propyl alcohol, isopropanol, ethylene glycol, propane diols, glycerine, toluene, ethylbenzene, dimethylbenzene, trimethylbenzene, dichloro
Methane, chloroform, tetrachloromethane, dioxane, tetrahydrofuran, 1-METHYLPYRROLIDONE, N,N-dimethylformamide and N,
One or more in N- dimethyl acetamides.
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Cited By (6)
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| CN108164667A (en) * | 2018-02-12 | 2018-06-15 | 清华大学 | A kind of porphyrin organic backbone membrane material and preparation method thereof |
| CN108219160A (en) * | 2018-02-12 | 2018-06-29 | 清华大学 | A kind of porphyrin organic backbone hybrid and preparation method thereof |
| CN109134830A (en) * | 2018-09-26 | 2019-01-04 | 台州学院 | A kind of covalent organic framework material and its preparation method and application that porphyrin-benzothiazole is difunctional |
| CN109967127A (en) * | 2019-03-06 | 2019-07-05 | 清华大学 | A kind of oxygen is precipitated and oxygen reduction reaction bifunctional catalyst and preparation method thereof |
| CN114907535A (en) * | 2022-05-27 | 2022-08-16 | 上海屹锂新能源科技有限公司 | COFs frame material and preparation method and application thereof |
| US11428440B2 (en) * | 2019-05-09 | 2022-08-30 | Uchicago Argonne, Llc | Method for making porphyrin covalent organic framework-based interface |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108164667A (en) * | 2018-02-12 | 2018-06-15 | 清华大学 | A kind of porphyrin organic backbone membrane material and preparation method thereof |
| CN108219160A (en) * | 2018-02-12 | 2018-06-29 | 清华大学 | A kind of porphyrin organic backbone hybrid and preparation method thereof |
| CN108219160B (en) * | 2018-02-12 | 2021-02-26 | 清华大学 | Porphyrin organic framework hybrid and preparation method thereof |
| CN108164667B (en) * | 2018-02-12 | 2021-02-26 | 清华大学 | Porphyrin organic framework membrane material and preparation method thereof |
| CN109134830A (en) * | 2018-09-26 | 2019-01-04 | 台州学院 | A kind of covalent organic framework material and its preparation method and application that porphyrin-benzothiazole is difunctional |
| CN109134830B (en) * | 2018-09-26 | 2021-01-29 | 台州学院 | Porphyrin-benzothiadiazole bifunctional covalent organic framework material and preparation method and application thereof |
| CN109967127A (en) * | 2019-03-06 | 2019-07-05 | 清华大学 | A kind of oxygen is precipitated and oxygen reduction reaction bifunctional catalyst and preparation method thereof |
| US11428440B2 (en) * | 2019-05-09 | 2022-08-30 | Uchicago Argonne, Llc | Method for making porphyrin covalent organic framework-based interface |
| CN114907535A (en) * | 2022-05-27 | 2022-08-16 | 上海屹锂新能源科技有限公司 | COFs frame material and preparation method and application thereof |
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| WO2019033611A1 (en) | 2019-02-21 |
| CN107641185B (en) | 2020-06-12 |
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